Thiophosphoric acid esters and their production



. as described above. Thus, this invention relates to 5 ethyl)l-0,0-dialkyl-thiol-(and thiono-thiol-) phosphoric States 2,952,700

I Patented Sept. 13,1950

295m 7' Y i i/ z V CHq-S-CHg-CH-S-P THIOPHOSPHORIC ACID ESTERS AND THEIR H3 PRODUCTION O OCH Walter Lorenz Wnppertal-Elberfeld and Gerhard '7 H J Schrader, wuppertal-Cronenberg, Germany, asc t S T S signors to Farbenfabriken Bayer Aktiengesell- 7 I Hi OCiHI schaft, Leverkusen, Germany, a corporation of V I I v fi/OCaH i G 10 4 om-s-cm-Cn-s-r "No Drawing. Filed Mal-.12, 1957, Ser. No. 645,403 5 Claims priority, application Germany Nov. 22,195 Y 1 The corresponding sulfoxyl and sulfonyl branched alkylene compounds as well as the corresponding thiolthiono analogs of the above mentioned thiol-phosphoric acid esters are, of course, also within the scopeof the present invention.

The preparation of these compounds may be effected by various methods. Thus, a general method for obtain- 12 Claims. Cl. 260-461) invention relates to and has as its objects new and useful thiophosphorlc acid esters and their production. More specifically this invention is concerned with 232 5 g" and dithiophosphofic acid-esters 9 the ing these compounds consists in reacting a salt of an 8 rm v V appropriate 0,0-dialkyl-thiol(or thlOIlO-IhlOD PhOSPhOI-f fif I ic acid with the desired alkyl-mercapto- (or sulfoxylor RYA,-SP sulfonyl-) alkyl halide as shown by the following equa- ER! OR: 11011: I. in which R, R and R stand for alkyl, especially lower 2 2 a ii alkyl radicals, A stands for a lower branched alkylenc :jf. f f chain, X standsforeither oxygen or sulfur and Y stands R: on: 1 OR for SISO 01.802" V V t p Q in these formulae R, R R X and Y have the same LThioand dithiophosphoric acid esters arefknown as effective insecticides and especially such compounds 'ofthe above indicated type in which the alkylene chain is not branched have become of special importancerecently. Considerable work has been done in' this field to find more effective and less toxic thiophosphoric acid esters of the above type.

3o significance as shown iabove, Hal stands for halogen and.

v Me for a salt forming radical. This method is known e.g. from German Patent 830,509 (alkylmercapto-alkylhalides as reaction compounds).

Other known methods, however, may also success fully be used to prepare the inventive compounds. Thus, dialkylphosphites may be reacted with the appropriate. In accordance Wlth the pres.ent pq there i alkyl thiocyanides or dialkylphosphoric or thionophosfound a new class of phoric acid-halides may be reacted with alkyl-mercaptoacid esters of the above general formula, particularly alkyl 7 mercaptans Also S (fi haloalkyl o,o dialkyl such tlllO- and dtthiophosphonc ac1d esters of the 40 h H hi ihi L) phosphoric acid esters may be formula reacted with suitable mercaptans, thus yielding the de- X sired alkylmercapto-branche d alkylesters. If sulfonyl- Q/ alkylesters are desired it is also possible to add ap'pro v v V priate vinylalkylsulfones to 0,0;dialkyl-thiol-(or thionof a 7 thiol-)-phosphoric acids or to react alkylsulfonylalkyl- 4 sulfohahdes wlth O,O-d1alkyl-phosphor1c aclds. -F1nally-,; m'whlch X and Y have the s-ame slgmficvanqesulfoxyl and sulfonylalkylesters may be prepared by oxidizing the corresponding alkylmercaptoalkylesters. This last method is described 'e.g'. in US. application Ser. No. 544,832 (sulfoxides) and Ser. No. 526,557 (sulfones). All the above mentioned'metho'ds of preparations refer to unbranched alkyl compounds. The inventive new esters may be prepared aecording to all these methods and by using exactly the amount of branched alkyl-reactant instead of the corresponding molecularamount of unbranched alkyl-compound.

S [alkylmerca1:ito-(sulffoxyl and sulfonyl-)-(branclied-- aeid esters. Without restricting this invention in any way, there may be mentioned as example the compounds T11 of the following formulae: A V Y 1. CH: 00H, a The new esters are generally valuable insecticides of o OCH; high activity and low toxicity." They may be used to L flies, mosquitos, aphids, mites and the-lik e." The ap r phcations may be etlected m the usual way 1.e. as other 0 9 phosphorous insecticides may be used. Thus, for example,

f concentrations from 0.00001% to about 1% are usually 1 fcinr-s-cnron--sr sufiicient" enough tof guarantee efiectivenessx The new I. I C v esters mayfurthermore be usedincombination witlr solid 0 0 CH and liquid carriers such as talc, chalk, bentonite, clayor t v a 3 water (if necessary with suitablecommercial emulsifiers) T- H-T ?P I alcohols, lower aliphatic hydrocarbons, aromatic hydro- (lint ooh, carbons etc. Most of the new vcompounds exhibit also my; strong systemic activity. The compounds, thus, maybe Il/f j brought incontactinany way with insects to bekilled or FT H. i plantstoibeprotectedgJ14; oi:

r Q QEZ Q'; :;-,;As-a.sp cial exampleiorthe ot someio ftheiins ventive compounds there are given below the activities of some compounds. The tests are carried out as follows:

' Spray solutions were prepared by dissolving the active ingredient in'the same amount of dimethylformamide. After having added about 10% this weight of a commercial emulsifier e.g. a benzyl hydroxydiphenyl polyglycol ether having about 15 glycol residues in its chain or a sultonated glycol ester of a long chain fatty acid, the organic solution is diluted with water to the concentrations indicated below. Forlthe'determination of toxicity rats were fed with baits containing the active ingredient. indicated below. The figures under toxicity, show from right to left the quantity of animals; tested/with symptoms/killed.

Toxicity 10 m kg. s/s/s (Rats orally) 25 lug/kg; 5/5/5-(LD 95) iwticidalvames mosquitolarvaenwli :001 70 systemic action on 0.1 100 black bean aphids.

s oo'iE'n V n/ CsBlrS0CH:--CHSP CH: 001m "Ioxicity -10 mg.-Ikg.3//5 g U I (Rats orally) -25 mg./kg.5/5/5 (LD 05) v i" r I Percent Percent fiies 0.1 100 grliidirb eshid 0 01- 132 ac .eanep s values mosquito-larvae, 0.001 100 systemic action on H 7 0]. 100

7 black bean aphids. q

/ fi/OCHr; CzHr-SQr-C:CH-SP V 1 cm :OCHI -T0xictty;..-'.' -100-mg:/lrg. 515 5 (L'Des (Bats orally) 7 I I Percent? Percent d flies---;- 0.1 100 I I V V blackbean aphids-.." 80 Goloradobeetles 40 a i d re es r i t si 0 m q to ae a 10o systemic act-ion on 1 I 100 black beanaphids.

The following -eramples are given by way of flflgen'only and without restrictingthe present invention Example]. V -0 o'c V m-s-cHT-{CH sTiV ...2: J ocr n 80 g. ammonium salt of 0,0-dim ethyI-thiol phospliorie airtime-dissolved in IQ water. -At 6t 3hereare to 96 g.

added slowly 74 g. (2 chloro-2'-methyl-et hyl(1)-) (ethyl-) sulfide. The temperature of 60 is kept for one further hour. 250 ml. benzeneare added and the benzene layer is separated, Washed twice with water and then dried over sodium sulfate (anhydrous). The benzene is distilled ed and the residue fractioiied in vacuo. Themain portion distills axe-011- ;mm. Hg at 83?, the yield -,Example2 V V o jozcsflr e msTcnfien sgr CH; ooarn 190-g. ammonium salt of 0,0-dipropyl-thiolphosphoric acidare dissolved in 300 ml. methanol. While stirring there are added slowly at 60"C. 148 'g'. '(Z-chlord-T- methyl-ethyl( l)-.) (ethyl-)sulfide. .The temperature is kept at 60 C. for one further hour and'then after cooling the reaction mixture is filtered with sulfur. The methanol isremoved by distillation and. the residue is taken up in. 500 ml. benzene and washed thrice with 50 ml. water. The benzene'layer then is dried over anhydrous sodium v p sulfate. After distilling oil the benzene the residue may be purified by vacuum' distillation. There are obtained 224 g. of the new ester of the above formula.

Example 3 CrHsS-CHrCH- S g t on. e. f 190 g. of an ammonium salt of diethylthiol phosphoric;

. acid :are dissolved in 400 of 98% alcohol, 140 g. of

2-chloro-2' -methylethylthioethyl ether are added at C;

The temperature isltept 'at '0. for one :hour, .the salts.

are filtered off with suction "and the methyl alcohol isseparated by distillation in vacuum. The residue is taken. up in .500 ml. of ether, the ethereal solution is washed twice with 50 ml. of water, dried and distilled- :175 g.

of the new ether ofB.P. 0.01 -mm./.92. 1C. are obtained as colorless water-insoluble oil. V

Example 4 V S OCH: Il/ mms-om-cm-s-r on. '0 CH1 17 g. of potassium hydroxide are dissolved in 50 ml.

- of water. 53 g. of dimethyl dithiophosphoric acid are action product is thoroughly shaken with 300 ml. of

benzene. The benzene solution is washed twice with-l00 ml. of water, separated and dried. After removing the benzene the new ester distills over under a pressure of 0.01 mm./ C. '35 :g. of'the ester are obtained as colorless water-insoluble oil."

Example 5 T methylethylthioethyl ether are added dropwise to the solution. The temperature is kept at 4'5" C., ior one hour. The solution is then cooled to room temperature, 300ml. of ether are added, the ethereal layer is separated,

- washed twice with l00 ml. each of water, dried and distilled- 49 g. of the new ester of the RP; 0.01 mm./ 104 C, are obtained'as water-insoluble colorless oil.

wise in form of a 30% aqueous solution so that a tem-' perature of 40-50 C. is maintained. The'solu'tion is stirred for another 30 minutes without heating. Excess hydrogen peroxide which may be presentin slight quantities, can be removed with bisulfite. The solution is diluted with 100 ml. of water and the acid is neutralized with dilute potassium carbonate solution. Some kiesel-' guhr is added and the crude product filtered off from a slight amount of a precipitate. The filtrate is mixed while stirring with solid potassium carbonate in a quantity so that the sulfoxide begins to precipitate. The precipitated ester is taken up in methylene chloride, the aqueous phase is shaken once more with methylene chloride, both methylene chloride solutions arecombined, dried with sodium sulfate and the solvent is removed in vacuum; 32 g. of the crude sulfoxide are obtained as colorless water-insoluble oil. The yield is 82.2% of the theoretical.

Example 7 CzH SO-CHf-OH-S-P (7H3 ocaHs 40 g. of. the sulfide group-containing ester of the following composition: I 00,11,

i CH3 OCaHs are dissolved in 75 ml. of methanol and mixed with 0.5 ml. of 50% sulfuric acid. Beginning at 20 C.; the calculated quantity of hydrogen peroxide (about 30%) is rapidly added in drops, the temperature rising to 4050 C. This temperature is maintained by cooling from outside. After the dropwise addition of the hydrogen peroxide cooling is stopped and the solution is allowed to cool. After about 30 minutes the reaction is complete. .The solution is diluted with 100 ml. of water, neutralized with potassium carbonate solution and'filteredf- The filtrate is mixed with cold, saturated potassium carbonate solution until the sulfoxide separates. The-sulfoxide is isolated by exhaustively extracting with methylene chloride. The methylene layer is dried with sodium sulfate and the methylene chloride removed by distillationjini-vacuum 3.8 g. of the new sulfoxide are obtained as colorless Watersoluble oil. The yield is 88% of the theoretical.

"' p 1 v soon; I

ll/ C2HsSO-GH:CHSP I v v H3 00H; To a solution of 31.2 g. (0.1 mol) of the'sulfide gro containing ester of the following composition: I

S OCH: 1 I j 7 I omss ourt ln s CH3 OCH:

the sulfide groups-containing peraturefor one hour. a .slight excess ofhydrogenfperox ide is removed withsodium bisulfitesolution'. The'solu- 1 413g. (0.15 mol) of the ester of the following position i v I vs ocgn,

' ll/ GzH5SCH:-(|JH-SP\ v CH3 OCgHs T I '3 are oxidized to the sulfoxide by addition of 75 ml. of methanol and 0.5 mol of 50% sulfuric acid with 15 m1. oil a hydrogen peroxide solution (about 30%) at40-50 C. After stirring for another 30 minutes; the solution is; diluted with water, the. excess acid' removed with dilute sodium'carbonate solution'and the precipitated oil "taken" upfinfbenzene. After working up as usual, 40.5 g. of the sulfoxide are obtained as "colorless water-insoluble oil; Yield: 89.7% of the theoretical. 51"..

Example 10 onnso- H,-oH-si ooH=),

41.8 g. (0.15 m l) ofthe ester of the following com position I HzCl are dissolved in ml. of water and 70 ml., of methanol. and mixed with 0.5 of*50% sulfuric acid. While cooling the calculated'quantity of hydrogenperoxide is added dropwise at 40-50". C. The solution is stirred for another 30'minutes without. heating. Slight amounts of hydrogen peroxide :are removed with bisulfit'e solutions After diluting the solution with'50' ml. of water, thesolu tion isadjusted to pH 6 with potassium .carbon'ate solution and the sulfoxide ester is extracted from the aqueous solution by repeatedly shaking with methylene chloride. After drying the solution over sodium sulfate, and dis. tilling off the solvent 38.3 g. of the crude sulfoxide ester are obtained as yellowish water-soluble oil. The yield is 86.8% of the theoretical.

Example "11 Y O H .T- H- i-= 5 omcl '.J'I.'."; 4? g. (0.15 mol) of the ester of the following com position HzCl i are suspended in dilute methanol "cQntaining OIS of sulfuric acid. Oxidizing is carried out with the calculated quantity of hydrogen peroxide at 40.-50 C. in the manner. The previously suspended ester 'dissolyesfpom pletely. 1The'solution is ,diluted water, adjustedto 'ffii -h qt m s tb na e sd h s l i d j is extracted fromthe solution byrep'eatedly shaking with methylene' chloi'ide. "After woi'king ='up as 42" the sulfoxide ester are obtained 'as yellowish, watensohr bie oil.-ield: 86.7% of the theoretical.

" 7 Example. 12 r added until the solution is colorless. The solution is then saturated with sulfate and the resulting sulfone ester taken up in methylene chloride by shaking." After distillingand drying, 36 g. of the sulfone are obtained as olor'less oil which is miscible with water. The purity of the crude product is satisfactory so that distillation is not ifeguired, prior to use. Yield: 88% of the theoretical. Example 13 1 O OCQH C:HsSOr-CHrCHSP CH1 OCQHs 16.2 g. (0.0595 .mol) of the sulfide group-contamin g qster ofthetollowing composition 7 7 mms-cm-o-s-r (His 0 C1 8 Example .15

CHaCl 31; g. (0.1 mol) ,of the ester ,of the following comr7 r o C;H -SCH:CHSL E =(O C255):

are added dropwise at 5-10 C. to a suspension or solu- V tion'of 142 g'. (0.0869 mol) of potassium permanganate and 12.7 g; (0.052mol) ofmagnesium sulfate in 200 m1. of water and :30 ml. of acetone. After stirring for another 30"minutes, sulfurous acid is introduced until the solution becomes 'colorlesa' The ester form is'separated by addition ofsodium sulfate and taken up in methylene chloride. J The methylene chloride layer is. dried'with sodium sulfate and the solvent removed by distillation in vacuum. i. J 15.8 g. of the new suifone are obtained as water-soluble, oil. The yield is 92.1% of'the theoretical.

38 g. (0.137 mol) of the ester'of the following composition .12:. ;:Il1i-7 .1"; fr? if 'J:

are added dropwise at 5- -10" "Cato a suspension of 35 g. of potassium permanganate and 33 g. of magnesium ini400 of water- The suspension is stirred at -C .;for. another v30 minutes and-sulfurous acid is then added untiltthe suspension becomes colorless.- .'I he'.pre c ip te sti in' 9 hs 4 e a ummer ape-obtained aspale yellow, viscous oil of limited y/ater filg i i yaillie nurse-w nt h mental.

V miscible water.

areaddeddropwise at .5.10 C. to a suspensionof 27 g. oil potassium permanganate and 22 got magnesium sulfate in 300 of water. After stirring at 5-10 Cgfor' 30 minutes; sulfurousjacid is introduceduntil the ganese' dioxide is discolored and the sulfone ester form is V separated by addition of sodium sulfate; By repeatedly shaking with methylene chloride, the ester is extracted from thesolution'. After drying and distilling; of the solvent, 2l g'. of the new sulfonc, ester are obtained as a' The yield is 62.8% of the theoreticali T .Efxample ld 7 on, OCH:

39 g. of the sulfoxide group-containing ester of the following composition r O OCH:

L (in, OCH:

are added dropwise at 5- 10 C. to a suspension of 33 g. (0.21 mol) of potassium permanganate and 32 g. (0.13 mol) of magnesium sulfate in 250 ml. of water and tat-acetone. The-suspension is stirred at 10 C. for another /2 hour. The manganese dioxide'which precipitates contains still a small .excms of potassium permanganate. Sulfurous acid is added to remove this until the solution is colorless. The solution is saturated with sodium sulfate and the resulting sulfone ester is extracted with methylene chloride. After distilling and drying, 3 3 g; of the sulfone are obtained as colorless oil whichis Example 17 V V lot/005E;

oimsor onr orks-r' .I I v CH; .OCaH; v v

17.5 giofthe sulfoxide groupcontainingester of the following composition Y a .OQOIHE n/ I Q!H 9' r- B are added dropwise at- 5 -10 C. to a suspension orsolw tion of l 4;2 gfipotassium permanganate and 12.7 g;' magnesium suliate'200 ml. of water andl30 ml. of acetone.

, Stirring is continued for-another 30'minutes and then 7 sulfurous acid is introduced until the solution becomes 'colorless. 'Ihe'ester is separated by the addition of ei v e ti a an f r e fid a PIQCdlII.'&',Of thepreceding examples is followed. 7

sodium sulfate and then takenup in "methylene chloride. The methylene chloride layer is dried with sodium sul fate and the solvent removed by distillation in ,vacuum.

-f f newjsulione are obtained as w tsnsbluble, viscous on. We claim: E

1. A thiophosphoric acid ester of the formula Elli/ 011. s ism 1 s aw:

yellowish oil whichdissolves in water only sparingly.

9 in which R and R stands for lower alkyl radicals, R stands for a member selected from the group consisting of lower alkyl and lower chloroalkyl, A stands for a lower alkylene chain of at least two carbon atoms, X stands for a member selected fi'om the group consisting of oxygen and sulfur, and Y stands for a member selected from the group consisting of S, SO and S0,.

2. A thiophosphoric acid ester of the formula I 0R R-Y-CHz-(FH-S-I R1 OR in which R, R and R stand for lower alkyl radicals, X stands for a member selected from the group consisting of oxygen and sulfur, and Y stands for a member selected from the group consisting of 8, SO and S0 3. A thiophosphoric acid ester of the formula in which R, R and R stand for lower alkyl radicals.

4. A thiophosphoric acid ester of the formula x OR II/ R-SO--GHCHSP R1 OR:

in which R, R and R stand for lower alkyl radicals, and X stands for a member selected from the group consisting of oxygen and sulfur.

5. A thiophosphoric acid ester of the formula 0 011* II/ RSO-GH:-CHSP in which R, R and R stand for lower alkyl radicals.

6. A thiophosphoric acid ester of the formula 5 on: H/ RSOCH(|)HSP R on:

in which R, R and R stand for lower alkyl radicals.

7. A thiophosphoric acid ester of the formula II/ R-SO:CH:CHSP

in which R, R and R stand for lower alkyl radicals, and X stands for a member selected from the group consisting of oxygen and sulfur.

8. A thiophosphoric acid ester of the formula 0 OCH:

9. A thiophosphoric acid ester of the formula ll cnns-cHr-cH-s-P H: OCH:

10. A thiophosphoric acid ester of the formula 11/ onns-om-cn-s-p 11. A thiophosphoric acid ester of the formula 12. A thiophosphoric acid ester of the formula CH; OCHI References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Bacon et al.: J. Am. Chem. Soc. 76, 670-676 (1954).

STATES EPATENT 'oFxfma v CERTIFICATION F CORRECTION 2.952 100 September 15 1960 atent No.

Walter Lorenz, et a1.

It is hereby cei'tified b a are in the above numbered patent requiring d Letters Patent should read as corrected below.

line 36 to 40 the formula should appear as the patent:

Column 7,

toad of as in shown below ins o oc n Signed and sealed Lhi (SEAL) Attest:

ERNEST we SWIDER DAVID L. LADD Commissioner of Patents Attesting Officer 

1. A THIOPHOSPHORIC ACID ESTER OF THE FORMULA 